Phosphorus-containing metal complexes

ABSTRACT

The present invention relates, inter alia, to metal complexes having improved solubility, to processes for the prepara ion of the metal complexes, to devices comprising these metal complexes and to the use of the metal complexes.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371)of PCT/EP2011/004418, filed Sep. 1, 2011, which claims benefit of Germanapplication 10 2010 046 512.7, filed Sep. 24, 2010 which are bothincorporated by reference.

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors are employed as functional materials isdescribed, for example, in U.S. Pat. No. 4,539,507, U.S. Pat. No.5,151,629, EP 0676461 and WO 98/27136. The emitting materials employedhere are increasingly organometallic complexes which exhibitphosphorescence instead of fluorescence (M. A. Baldo et al., Appl. Phys.Lett. 1999, 75, 4-6). For quantum-mechanical reasons, an up to four-foldenergy and power efficiency is possible using organometallic compoundsas phosphorescence emitters. In general, however, there is still a needfor improvement in OLEDs which exhibit triplet emission, in particularwith respect to efficiency, operating voltage and lifetime. Thisapplies, in particular, to OLEDs which emit in the relatively short-waveregion, i.e. green and blue. Furthermore, many phosphorescent emittersdo not have adequate solubility for processing from solution, meaningthat there is also a further need for improvement here.

In accordance with the prior art, the triplet emitters employed inphosphorescent OLEDs are, in particular, iridium and platinum complexes,which are usually employed as cyclometallated complexes. The ligandshere are frequently derivatives of phenylpyridine. However, thesolubility of such complexes is frequently low, which makes processingfrom solution more difficult or prevents it completely.

The prior art discloses iridium complexes which are substituted by anoptionally substituted aryl or heteroaryl group on the phenyl ring ofthe phenylpyridine ligand in the para-position to the coordination tothe metal (WO 2004/026886 A2). Improved solubility of the complexes wasthereby achieved. However, there is also still a further need forimprovement here with respect to the solubility and the efficiency andlifetime of the complexes.

Surprisingly, it has been found that certain metal chelate complexesdescribed in greater detail below have improved solubility andfurthermore result in improvements in the organic electroluminescentdevice, in particular with respect to the efficiency and lifetime. Thepresent invention therefore relates to these metal complexes and toorganic electroluminescent devices which comprise these complexes.

The invention relates to a compound of the formula (1),M(L)_(n)(L′)_(m)  formula (1)where the compound of the general formula (1) contains a moiety M(L)_(n)of the formula (2):

where M is bonded to any desired bidentate ligand L via a nitrogen atomN and via a carbon atom C andwhere A can be any desired heteroaromatic condensed ring system andwhere B can be any desired aromatic or heteroaromatic ring or anydesired aromatic or heteroaromatic ring system, which is condensedand/or non-condensed, andwhere the following applies to the symbols and indices used:

-   M is a metal selected from the group consisting of iridium, rhodium,    platinum, palladium, osmium and ruthenium, preferably iridium,    rhodium, platinum and palladium;-   L′ is, identically or differently on each occurrence, any desired    co-ligand;-   W is, identically or differently on each occurrence, a radical of    the formulae (3) and (4)

-   -   where V is equal to S or O;

-   R⁴ is, identically or differently on each occurrence, H, D, F, Cl,    Br, I, N(R²)₂, a straight-chain alkyl, alkoxy or thioalkoxy group    having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group    having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl,    alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C    atoms, each of which may be substituted by one or more radicals R²,    where one or more non-adjacent CH₂ groups may be replaced by    R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se, C═NR²,    P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more H atoms    may be replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or    heteroaromatic ring system having 5 to 60 aromatic ring atoms, which    may in each case be substituted by one or more radicals R², or an    aryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy group having 5 to    60 aromatic ring atoms, which may be substituted by one or more    radicals R², or a diarylamino group, diheteroarylamino group or    arylheteroarylamino group having 10 to 40 aromatic ring atoms, which    may be substituted by one or more radicals R², or a combination of    two or more of these groups; two or more radicals R⁴ here may also    form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused    ring system with one another;

-   R² is, identically or differently on each occurrence, H, D, F, Cl,    Br, I, N(R³)₂, CN, NO₂, Si(R³)₃, B(OR³)₂, C(═O)R³, P(═O)(R³)₂,    S(═O)R³, S(═O)₂R³, OSO₂R³, a straight-chain alkyl, alkoxy or    thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl    or alkynyl group having 2 to 40 C atoms or a branched or cyclic    alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group    having 3 to 40 C atoms, each of which may be substituted by one or    more radicals R³, where one or more non-adjacent CH₂ groups may be    replaced by R³C═CR³, C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se,    C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and where one or more    H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or an    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more radicals    R³, or an aryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy group    having 5 to 60 aromatic ring atoms, which may be substituted by one    or more radicals R³, or a diarylamino group, diheteroarylamino group    or arylheteroarylamino group having 10 to 40 aromatic ring atoms,    which may be substituted by one or more radicals R³, or a    combination of two or more of these groups; two or more adjacent    radicals R² here may form a mono- or polycyclic, aliphatic or    aromatic ring system with one another;

-   R³ is, identically or differently on each occurrence, H, D, F or an    aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having    1 to 20 C atoms, in which, in addition, one or more H atoms may be    replaced by F; two or more substituents R³ here may also form a    mono- or polycyclic, aliphatic or aromatic ring system with one    another;

-   q is an integer greater than or equal to 0;

-   p is an integer greater than or equal to 0; with the proviso that    p+q is an integer greater than or equal to 1;

-   n is 1, 2 or 3 for M equal to iridium or rhodium and is 1 or 2 for M    equal to platinum or palladium;

-   m is 0, 1, 2, 3 or 4;    the indices n and m here are selected so that the coordination    number on the metal corresponds to 6 for M equal to iridium or    rhodium and corresponds to 4 for M equal to platinum or palladium;    a plurality of ligands L here may also be linked to one another or L    may be linked to L′ via any desired bridge Z and thus form a    tridentate, tetradentate, pentadentate or hexadentate ligand system.

In a preferred embodiment of the present invention, the ligands L arenot bridged with one another, neither are the ligands L bridged with theligands L′.

In a further preferred embodiment of the present invention, M(L)_(n)from formula (1) is equal to the formulae (5) or (6).

In a very preferred embodiment of the present invention, M(L)_(n) fromformula (1) is equal to the formulae (7) and (8).

In a further preferred embodiment of the present invention, M(L)_(n)from formula (1) is equal to the formula (9).

where the following applies to the symbols in indices used:

-   X is, identically or differently on each occurrence, CR¹ or N;-   Q is, identically or differently on each occurrence, R¹C═CR¹, R¹C═N,    O, S, Se or NR¹;-   R¹ is, identically or differently on each occurrence, H, D, F, Cl,    Br, I, N(R²)₂, CN, NO₂, Si(R²)₃, B(OR²)₂, C(═O)R², P(═O)(R²)₂,    S(═O)R², S(═O)₂R², OSO₂R², a straight-chain alkyl, alkoxy or    thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl    or alkynyl group having 2 to 40 C atoms or a branched or cyclic    alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group    having 3 to 40 C atoms, each of which may be substituted by one or    more radicals R², where one or more non-adjacent CH₂ groups may be    replaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se,    C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more    H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or an    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more radicals    R², or an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60    aromatic ring atoms, which may be substituted by one or more    radicals R², or a diarylamino group, diheteroarylamino group or    arylheteroarylamino group having 10 to 40 aromatic ring atoms, which    may be substituted by one or more radicals R², or a combination of    two or more of these groups; two or more radicals R¹ here may also    form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused    ring system with one another. For the other symbols and indices, the    above definitions apply.

Preference is furthermore given for the purposes of the invention tomoieties M(L)_(n) having the formula (10)

where the equation p=r+s applies to the indices r and s and, owing top+q≧1, r+s+q≧1 also applies, and the aromatic or heteroaromatic ring D,which is condensed onto C in any desired and possible manner, where Dcan be an aromatic or heteroaromatic ring or an aromatic orheteroaromatic condensed and/or non-condensed ring system.

In a further preferred embodiment of the present invention, the ring Dis an aromatic or heteroaromatic ring system having 5 to 60 aromaticring atoms, which may in each case be substituted by one or moreradicals R², or an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which may be substituted by one or more radicalsR², or a diarylamino group, diheteroarylamino group orarylheteroarylamino group having 10 to 40 aromatic ring atoms, which maybe substituted by one or more radicals R², or a combination of two ormore of these groups; two or more radicals R¹ here may also form a mono-or polycyclic, aliphatic, aromatic and/or benzo-fused ring system withone another.

In a particularly preferred embodiment of the present invention, thering D is equal to the formula (11)

In a very particularly preferred embodiment of the present invention,the moiety M(L)_(n) of the formula (1) is selected from the followingformulae (12) to (17)

Furthermore preferred embodiments for the purposes of the presentinvention are moieties M(L)_(n) of the formula (1) having the formulae(18) to (23)

It is furthermore particularly preferred for the purposes of the presentinvention for the radical Q to be either S or R¹C═CR¹.

Very preferred embodiments of the present invention are compounds of theformula (1) containing the moieties M(L)_(n) of the following formulae(24) to (29).

Very particularly preferred embodiments of the present invention arecompounds of the formula (1) containing the moieties M(L)_(n) of thefollowing formulae (30) to (35).

In an especially preferred embodiment of the present invention, q+r+s=1.

Preference is furthermore given for the purposes of the presentinvention to compounds of the formula (1) containing the moiety M(L)_(n)characterised in that r=0 and thus: q+s≧1. In a very preferredembodiment of the present invention: q+s=1, where the radical W can beat any desired and possible position of the rings and replaces thesubstituent R¹ there. If the radical W is bonded to the ligand via X, Xis equal to CR¹ and the radical W again replaces the radical R¹.

Particular preference is given for the purposes of the present inventionto compounds of the formula (1) containing the moiety M(L)_(n) of theformulae (36) to (59).

Very particularly preferred embodiments of the present invention arefurthermore compounds of the formula (1) containing a moiety M(L)_(n) ofthe formulae (36), (37), (40), (41), (44), (45), (48), (49), (52), (53),(56) and (57).

Very particularly preferred embodiments of the present invention arealso compounds of the formula (1) containing a moiety M(L)_(n) of theformulae (36), (37), (40) and (41).

Especially preferred embodiments of the present invention are compoundsof the formula (1) containing a moiety M(L)_(n) of the formulae (36) and(40).

The substituents R¹ can result in a bridge within a ligand L whichresult in further stiffening of the ligand. Preferred embodiments in thesense of the invention are the formulae (60) to (97).

In an especially preferred embodiment of the present invention, X isequal to CR¹.

In a further preferred embodiment of the present invention, R¹ is,identically or differently on each occurrence, H, D, F, Cl, Br, I,N(R²)₂, CN, NO₂, a straight-chain alkyl, alkoxy or thioalkoxy grouphaving 1 to 40 C atoms or a straight-chain alkenyl or alkynyl grouphaving 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl,alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may besubstituted by one or more radicals R², where one or more non-adjacentCH₂ groups may be replaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂,C═O, C═S, C═Se, C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and whereone or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,which may be substituted by one or more radicals R², or a diarylaminogroup, diheteroarylamino group or arylheteroarylamino group having 10 to40 aromatic ring atoms, which may be substituted by one or more radicalsR², or a combination of two or more of these groups; two or moreradicals R¹ here may also form a mono- or polycyclic, aliphatic,aromatic and/or benzofused ring system with one another.

In a further very preferred embodiment of the present invention, themoiety M(L)_(n) of the compounds of the formula (1) is selected from theformulae (98) to (109).

Very particular preference is given here to the formulae (98), (99),(100), (101), (101a), (101b), (102), (103), (104), (105), (105a),(105b), (106), (107), (108), (109), (109a) and (109b). Very particularpreference is furthermore given to the formulae (98), (99), (100),(101), (102), (103), (104), (105), (106), (107), (108) and (109). Theformulae (98) and (99) are especially preferred here.

In a preferred embodiment of the present invention, the radical W isselected from the radicals of the formulae (110) to (115).

where

-   R⁵ is, identically or differently on each occurrence, H, D, a    straight-chain alkyl or thioalkoxy group having 1 to 40 C atoms or a    straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a    branched or cyclic alkyl, alkenyl, alkynyl or thioalkoxy group    having 3 to 40 C atoms, each of which may be substituted by one or    more radicals R², where one or more non-adjacent CH₂ groups may be    replaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se,    C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more    H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or an    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more radicals    R², or an aryloxy or heteroaryloxy group having 5 to 60 aromatic    ring atoms, which may be substituted by one or more radicals R², or    a diarylamino group, diheteroarylamino group or arylheteroarylamino    group having 10 to 40 aromatic ring atoms, which may be substituted    by one or more radicals R², or a combination of two or more of these    groups; two or more radicals R¹ here may also form a mono- or    polycyclic, aliphatic, aromatic and/or benzo-fused ring system with    one another and    the hyphen has the same meaning as everywhere else within the    present invention. It denotes the bond from the radical to the    ligand.

In a very preferred embodiment of the present invention, the radical Wis equal to the formula (110).

In a preferred embodiment of the present invention, the radical R⁵ is,identically or differently on each occurrence, H, D, a straight-chainalkyl group having 1 to 40 C atoms or a straight-chain alkenyl oralkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl,alkenyl, alkynyl group having 3 to 40 C atoms, each of which may besubstituted by one or more radicals R², where one or more non-adjacentCH₂ groups may be replaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂,C═O, C═S, C═Se, C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and whereone or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,which may be substituted by one or more radicals R², or a diarylaminogroup, diheteroarylamino group or arylheteroarylamino group having 10 to40 aromatic ring atoms, which may be substituted by one or more radicalsR², or a combination of two or more of these groups; two or moreradicals R¹ here may also form a mono- or polycyclic, aliphatic,aromatic and/or benzo-fused ring system with one another and

In a very preferred embodiment of the present invention, the radical R⁵is selected from the formulae (116) to (286), where the formulaeindicated may themselves be substituted by one or more radicals R³,which may be identical or different on each occurrence.

An aryl group in the sense of this invention contains 6 to 40 C atoms; aheteroaryl group in the sense of this invention contains 2 to 40 C atomsand at least one heteroatom, with the proviso that the sum of C atomsand heteroatoms is at least 5. The heteroatoms are preferably selectedfrom N, O and/or S. An aryl group or heteroaryl group here is taken tomean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed aryl or heteroaryl group, for example naphthalene,anthracene, phenanthrene, quinoline, isoquinoline, etc.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 2 to 60 C atoms and at least one heteroatom inthe ring system, with the proviso that the sum of C atoms andheteroatoms is at least 5. The heteroatoms are preferably selected fromN, O and/or S. For the purposes of this invention, an aromatic orheteroaromatic ring system is intended to be taken to mean a systemwhich does not necessarily contain only aryl or heteroaryl groups, butinstead in which, in addition, a plurality of aryl or heteroaryl groupsmay be interrupted by a non-aromatic unit (preferably less than 10% ofthe atoms other than H), such as, for example, an sp³-hybridised C, N orO atom or a carbonyl group. Thus, for example, systems such as9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether,stilbene, etc., are also intended to be taken to mean aromatic ringsystems for the purposes of this invention, and likewise systems inwhich two or more aryl groups are interrupted, for example, by a linearor cyclic alkyl group or by a silyl group.

A cyclic alkyl, alkoxy or thioalkoxy group in the sense of thisinvention is taken to mean a monocyclic, bicyclic or polycyclic group.

For the purposes of the present invention, a C₁- to C₄₀-alkyl group, inwhich, in addition, individual H atoms or CH₂ groups may be substitutedby the above-mentioned groups, is taken to mean, for example, theradicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, tert-pentyl, 2-pentyl,cyclopentyl, n-hexyl, s-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, cyclohexyl,2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl,1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl,1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl,3-(3,7-dimethyl)octyl, trifluoromethyl, pentafluoroethyl or2,2,2-trifluoroethyl. An alkenyl group is taken to mean, for example,ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl,cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl orcyclooctadienyl. An alkynyl group is taken to mean, for example,ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. AC₁- to C₄₀-alkoxy group is taken to mean, for example, methoxy,trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,s-butoxy, t-butoxy or 2-methylbutoxy. An aromatic or heteroaromatic ringsystem having 5-60 aromatic ring atoms, which may also in each case besubstituted by the radicals R mentioned above and which may be linked tothe aromatic or heteroaromatic ring system via any desired positions, istaken to mean, for example, groups derived from benzene, naphthalene,anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene,chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene,pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene,fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene,tetrahydropyrene, cis- or trans-indenofluorene, cis- ortrans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene,truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran,isobenzofuran, dibenzofuran, thiophene, benzothiophene,isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole,carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,phenothiazine, phenoxazine, pyrazole, indazole, imidazole,benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine,benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene,2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole.

The compounds of the formula (1) may be electrically charged oruncharged. In a preferred embodiment, the compounds of the formula (1)are electrically neutral. This is achieved in a simple manner in thatthe charges of the ligands L and L′ are selected so that they compensatefor the charge of the complexed metal atom M.

Preference is furthermore given to compounds of the formula (1),characterised in that the sum of the valence electrons around the metalatom is 16 for platinum and palladium and 18 for iridium and rhodium.This preference is due to the particular stability of these metalcomplexes.

In a preferred embodiment of the invention, M stands for iridium orplatinum. M particularly preferably stands for iridium.

If M stands for platinum or palladium, the index n stands for 1 or 2. Ifthe index n=1, one bidentate or two monodentate ligands L′, preferablyone bidentate ligand L′, are also coordinated to the metal M.Correspondingly, the index m=1 for one bidentate ligand L′ and the indexm=2 for two monodentate ligands L′. If the index n=2, the index m=0.

If M stands for iridium or rhodium, the index n stands for 1, 2 or 3,preferably for 2 or 3 and particularly preferably for 3. If the indexn=1, four monodentate or two bidentate or one bidentate and twomonodentate or one tridentate and one monodentate or one tetradentateligand L′, preferably two bidentate ligands L′, are also coordinated tothe metal. Correspondingly, the index m is, depending on the ligand L′,equal to 1, 2, 3 or 4. If the index n=2, one bidentate or twomonodentate ligands L′, preferably one bidentate ligand L′, are alsocoordinated to the metal. Correspondingly, the index m is, depending onthe ligand L′, equal to 1 or 2. If the index n=3, the index m=0.

In a further preferred embodiment of the invention, either all symbols Xstand, identically or differently on each occurrence, for CR¹ or allsymbols X stand for N.

In a further preferred embodiment of the invention, the symbol Q stands,identically or differently on each occurrence, for R¹C═CR¹, R¹C═N, O orNR¹, particularly preferably for R¹C═CR¹ and R¹C═N and especiallypreferably for R¹C═CR¹.

It is particularly preferred for the above-mentioned preferences toapply simultaneously.

In a particularly preferred embodiment of the invention, the followingapplies to the symbols used:

-   M is iridium or platinum, particularly preferably iridium;-   X is on each occurrence CR¹ for all positions which are not bonded    directly to M;-   Q is, identically or differently on each occurrence, R¹C═CR¹ or    R¹C═N, particularly preferably R¹C═CR¹;

Where the symbols and indices used have the meanings mentioned above, inparticular the preferred meanings mentioned above.

The compounds of the formula (1) according to the invention can beheteroleptic or homoleptic complexes. Preferred embodiments of thepresent invention are homoleptic complexes where m=0.

In the case of heteroleptic complexes of the formula (1), a bridgingunit Z which links the ligand L to one or more further ligands L or L′may also be present on one of the radicals R¹. In a preferred embodimentof the invention, a bridging unit Z is present instead of one of theradicals R¹, meaning that the ligands have a tridentate or polydentateor polypodal character. Two bridging units Z of this type may also bepresent. This results in the formation of macrocyclic ligands or in theformation of cryptates.

Preferred structures having polydentate ligands are the metal complexesof the following formulae (287) to (298):

where the symbols used have the meanings mentioned above, and Zpreferably represents a bridging unit containing 1 to 80 atoms from thethird, fourth, fifth and/or sixth main group (IUPAC group 13, 14, 15 or16) or a 3- to 6-membered homo- or heterocycle which covalently bondsthe part-ligands L to one another or L to L′. The bridging unit Z heremay also have an asymmetric structure, i.e. the linking of Z to L or L′need not be identical.

The bridging unit Z may be neutral, singly, doubly or triply negativelycharged or singly, doubly or triply positively charged. Z is preferablyneutral or singly negatively charged or singly positively charged. Thecharge of Z here is preferably selected so that overall a neutralcomplex arises.

If Z is a trivalent group, i.e. bridges three ligands L to one anotheror two ligands L to L′ or one ligand L to two ligands L′, Z ispreferably selected, identically or differently on each occurrence, fromthe group consisting of B, B(R²)⁻, B(C(R²)₂)₃, (R²)B(C(R²)₂)₃ ⁻, B(O)₃,(R²)B(O)₃ ⁻, B(C(R²)₂C(R²)₂)₃, (R²)B(C(R²)₂C(R²)₂)₃ ⁻, B(C(R²)₂O)₃,(R²)B(C(R²)₂O)₃ ⁻, B(OC(R²)₂)₃, (R²)B(OC(R²)₂)₃, C(R²), CO⁻, CN(R²)₂,(R²)C(C(R²)₂)₃, (R²)C(O)₃, (R²)C(C(R²)₂C(R²)₂)₃, (R²)C(C(R²)₂O)₃,(R²)C(OC(R²)₂)₃, (R²)C(Si(R²)₂)₃, (R²)C(Si(R²)₂C(R²)₂)₃,(R²)C(C(R²)₂Si(R²)₂)₃, (R²)C(Si(R²)₂Si(R²)₂)₃, Si(R²), (R²)Si(C(R²)₂)₃,(R²)Si(O)₃, (R²)Si(C(R²)₂C(R²)₂)₃, (R²)Si(OC(R²)₂)₃, (R²)Si(C(R²)₂O)₃,(R²)Si(Si(R²)₂)₃, (R²)Si(Si(R²)₂C(R²)₂)₃, (R²)Si(C(R²)₂Si(R²)₂)₃,(R²)Si(Si(R²)₂Si(R²)₂)₃, N, NO, N(R²)⁺, N(C(R²)₂)₃, (R²)N(C(R²)₂)₃ ⁺,N(C═O)₃, N(C(R²)₂C(R²)₂)₃, (R²)N(C(R²)₂C(R²)₂)⁺, P, P(R²)⁺, PO, PS, PSe,PTe, P(O)₃, PO(O)₃, P(OC(R²)₂)₃, PO(OC(R²)₂)₃, P(C(R²)₂)₃,P(R²)(C(R²)₂)₃ ⁺, PO(C(R²)₂)₃, P(C(R²)₂C(R²)₂)₃, P(R²) (C(R²)₂C(R²)₂)₃⁺, PO(C(R²)₂C(R²)₂)₃, S⁺, S(C(R²)₂)₃ ⁺, S(C(R²)₂C(R²)₂)₃ ⁺, or a unit ofthe formula (299), (300), (301) or (302),

where the dashed bonds in each case indicate the bonding to thepart-ligands L or L′, and A is selected, identically or differently oneach occurrence, from the group consisting of a single bond, O, S,S(═O), S(═O)₂, NR², PR², P(═O)R², P(═NR²), C(R²)₂, C(═O), C(═NR²),C(═C(R²)₂), Si(R²)₂ or BR². The other symbols used have the meaningsmentioned above.

If Z is a divalent group, i.e. bridges two ligands L to one another orone ligand L to L′, Z is preferably selected, identically or differentlyon each occurrence, from the group consisting of BR², B(R²)₂ ⁻, C(R²)₂,C(═O), Si(R²)₂, NR², PR², P(R²)₂ ⁺, P(═O)(R²), P(═S)(R²), AsR²,As(═O)(R²), As(═S)(R²), O, S, Se, or a unit of the formulae (303) to(311),

where the dashed bonds in each case indicate the bonding to the partligands L or L′, and the further symbols used in each case have themeanings mentioned above.

Preferred ligands L′ as occur in formula (1) are described below.Correspondingly, the ligand groups L′ can also be selected if they arebonded to L via a bridging unit Z.

The ligands L′ are preferably neutral, monoanionic, dianionic ortrianionic ligands, particularly preferably neutral or monoanionicligands. They can be monodentate, bidentate, tridentate or tetradentateand are preferably bidentate, i.e. preferably have two coordinationsites. As described above, the ligands L′ may also be bonded to L via abridging group Z.

Preferred neutral, monodentate ligands L′ are selected from carbonmonoxide, nitrogen monoxide, alkyl cyanides, such as, for example,acetonitrile, aryl cyanides, such as, for example, benzonitrile, alkylisocyanides, such as, for example, methyl isonitrile, aryl isocyanides,such as, for example, benzoisonitrile, amines, such as, for example,trimethylamine, triethylamine, morpholine, phosphines, in particularhalophosphines, trialkylphosphines, triarylphosphines oralkylarylphosphines, such as, for example, trifluorophosphine,trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine,triphenylphosphine, tris(pentafluorophenyl)phosphine, phosphites, suchas, for example, trimethyl phosphite, triethyl phosphite, arsines, suchas, for example, trifluoroarsine, trimethylarsine, tricyclohexylarsine,tri-tert-butylarsine, triphenylarsine, tris(pentafluorophenyl)arsine,stibines, such as, for example, trifluorostibine, trimethylstibine,tricyclohexylstibine, tri-tert-butylstibine, triphenylstibine,tris(pentafluorophenyl)stibine, nitrogen-containing heterocycles, suchas, for example, pyridine, pyridazine, pyrazine, pyrimidine, triazine,and carbenes, in particular Arduengo carbenes.

Preferred monoanionic, monodentate ligands L′ are selected from hydride,deuteride, the halides F⁻, Cl⁻, Br⁻ and I⁻, alkylacetylides, such as,for example, methyl-C≡C⁻, tert-butyl-C≡C⁻, arylacetylides, such as, forexample, phenyl-C≡C⁻, cyanide, cyanate, isocyanate, thiocyanate,isothiocyanate, aliphatic or aromatic alcoholates, such as, for example,methanolate, ethanolate, propanolate, isopropanolate, tert-butylate,phenolate, aliphatic or aromatic thioalcoholates, such as, for example,methanethiolate, ethanethiolate, propanethiolate, isopropanethiolate,tert-butanethiolate, thiophenolate, amides, such as, for example,dimethylamide, diethylamide, diisopropylamide, morpholide, carboxylates,such as, for example, acetate, trifluoroacetate, propionate, benzoate,aryl groups, such as, for example, phenyl, naphthyl, and anionic,nitrogen-containing heterocycles, such as pyrrolide, imidazolide,pyrazolide. The alkyl groups in these groups are preferably C₁-C₂₀-alkylgroups, particularly preferably C₁-C₁₀-alkyl groups, very particularlypreferably C₁-C₄-alkyl groups. An aryl group is also taken to meanheteroaryl groups. These groups are as defined above.

Preferred di- or trianionic ligands are O²⁻, S²⁻, carbides, which resultin coordination in the form R—C≡M, and nitrenes, which result incoordination in the form R—N=M, where R generally stands for asubstituent, or N³⁻.

Preferred neutral or mono- or dianionic, bidentate or polydentateligands L′ are selected from diamines, such as, for example,ethylenediamine, N,N,N′,N′-tetramethylethylenediamine, propylenediamine,N,N,N′,N′-tetra-methylpropylenediamine, cis- ortrans-diaminocyclohexane, cis- ortrans-N,N,N′,N′-tetramethyldiaminocyclohexane, imines, such as, forexample, 2-[1-(phenylimino)ethyl]pyridine,2-[1-(2-methylphenylimino)ethyl]pyridine,2-[1-(2,6-diisopropylphenylimino)ethyl]pyridine,2-[1-(methylimino)ethyl]-pyridine, 2-[1-(ethylimino)ethyl]pyridine,2-[1-(isopropylimino)ethyl]pyridine,2-[1-(tert-butylimino)ethyl]pyridine, diimines, such as, for example,1,2-bis(methylimino)ethane, 1,2-bis(ethylimino)ethane,1,2-bis(isopropylimino)ethane, 1,2-bis(tert-butylimino)ethane,2,3-bis(methylimino)butane, 2,3-bis(ethylimino)butane,2,3-bis(isopropylimino)butane, 2,3-bis(tert-butylimino)butane,1,2-bis(phenylimino)ethane, 1,2-bis(2-methylphenylimino)ethane,1,2-bis(2,6-diisopropylphenylimino)ethane,1,2-bis(2,6-di-tert-butylphenylimino)ethane, 2,3-bis(phenylimino)butane,2,3-bis(2-methylphenylimino)butane,2,3-bis(2,6-diisopropylphenylimino)butane,2,3-bis(2,6-di-tert-butylphenylimino)butane, heterocycles containing twonitrogen atoms, such as, for example, 2,2′-bipyridine, o-phenanthroline,diphosphines, such as, for example, bisdiphenylphosphinomethane,bisdiphenylphosphinoethane, bis(diphenylphosphino)propane,bis(diphenylphosphino)butane, bis(dimethylphosphino)methane,bis(dimethylphosphino)ethane, bis(dimethylphosphino)propane,bis(diethylphosphino)methane, bis(diethylphosphino)ethane,bis(diethylphosphino)propane, bis(di-tert-butylphosphino)methane,bis(di-tert-butylphosphino)ethane, bis(tert-butylphosphino)propane,1,3-diketonates derived from 1,3-diketones, such as, for example,acetylacetone, benzoylacetone, 1,5-diphenylacetylacetone,dibenzoylmethane, bis(1,1,1-trifluoroacetyl)methane, 3-ketonates derivedfrom 3-ketoesters, such as, for example, ethyl acetoacetate,carboxylates derived from aminocarboxylic acids, such as, for example,pyridine-2-carboxylic acid, quinoline-2-carboxylic acid, glycine,N,N-dimethylglycine, alanine, N,N-dimethylaminoalanine, salicyliminatesderived from salicylimines, such as, for example, methylsalicylimine,ethylsalicylimine, phenylsalicylimine, dialcoholates derived fromdialcohols, such as, for example, ethylene glycol, 1,3-propylene glycol,and dithiolates derived from dithiols, such as, for example,1,2-ethylenedithiol, 1,3-propylenedithiol.

Preferred tridentate ligands are borates of nitrogen-containingheterocycles, such as, for example, tetrakis(1-imidazolyl)borate andtetrakis-(1-pyrazolyl)borate.

Particular preference is furthermore given to bidentate, monoanionicligands L′ which form, with the metal, a cyclometallated five-memberedor six-membered ring having at least one metal-carbon bond, inparticular a cyclometallated five-membered ring. These are, inparticular, ligands as generally used in the area of phosphorescentmetal complexes for organic electroluminescent devices, i.e. ligands ofthe phenylpyridine, naphthylpyridine, phenylquinoline,phenylisoquinoline, etc., type, each of which may be substituted by oneor more radicals R¹ to R⁷. A multiplicity of ligands of this type isknown to the person skilled in the art in the area of phosphorescentelectroluminescent devices, and he will be able to select furtherligands of this type, without inventive step, as ligand L′ for compoundsof the formula (1). In general, the combination of two groups, asrepresented by the following formulae (312) to (339), is particularlysuitable for this purpose, where one group is bonded via a neutralnitrogen atom or a carbene atom and the other group is bonded via anegatively charged carbon atom or a negatively charged nitrogen atom.The ligand L′ can then be formed from the groups of the formulae (312)to (339) by these groups bonding to one another, in each case at theposition denoted by #. The position at which the groups coordinate tothe metal is denoted by *. These groups may also be bonded to the ligandL via one or two bridging units Z.

The symbols used here have the same meaning as described above, andpreferably a maximum of three symbols X in each group stand for N,particularly preferably a maximum of two symbols X in each group standfor N, very particularly preferably a maximum of one symbol X in eachgroup stands for N. Especially preferably, all symbols X stand,identically or differently on each occurrence, for CR¹.

In a particularly preferred embodiment of the present invention, twofragments of a ligand L′ of the formulae (312) to (339) are combinedwith one another via position # in such a way that at least one of thefragments contains a heteroatom at position *.

In a very particularly preferred embodiment of the present invention,the ligand L′ is composed of precisely one fragment with no heteroatomfrom the list of the formulae (312) to (339) and precisely one fragmentwith a heteroatom, preferably a nitrogen atom, from the list of thefragments having the formulae (312) to (339).

Likewise preferred ligands L′ are η⁵-cyclopentadienyl,η⁵-pentamethylcyclopentadienyl, η⁶-benzene and η⁷-cycloheptatrienyl,each of which may be substituted by one or more radicals R¹.

Likewise preferred ligands L′ are 1,3,5-cis-cyclohexane derivatives, inparticular of the formula (340), 1,1,1-tri(methylene)methanederivatives, in particular of the formula (341), and1,1,1-trisubstituted methanes, in particular of the formulae (342) and(343),

where, in each of the formulae, the coordination to the metal M isdepicted, R¹ has the meaning mentioned above, and A stands, identicallyor differently on each occurrence, for O⁻, S⁻, COO⁻, P(R¹)₂ or N(R¹)₂.

Preferred radicals R¹ in the structures mentioned above are selected oneach occurrence, identically or differently, from the group consistingof H, D, F, Br, N(R²)₂, CN, B(OR²)₂, C(═O)R², P(═O)(R²)₂, astraight-chain alkyl group having 1 to 10 C atoms or a straight-chainalkenyl or alkynyl group having 2 to 10 C atoms or a branched or cyclicalkyl, alkenyl or alkynyl group having 3 to 10 C atoms, each of whichmay be substituted by one or more radicals R², where one or more H atomsmay be replaced by F, or an aromatic or heteroaromatic ring systemhaving 5 to 14 aromatic ring atoms, which may in each case besubstituted by one or more radicals R²; a plurality of radicals R¹ heremay also form a mono- or polycyclic, aliphatic, aromatic and/orbenzo-fused ring system with one another. Particularly preferredradicals R¹ are selected on each occurrence, identically or differently,from the group consisting of H, F, Br, CN, B(OR²)₂, a straight-chainalkyl group having 1 to 6 C atoms, in particular methyl, or a branchedor cyclic alkyl group having 3 to 10 C atoms, in particular isopropyl ortertbutyl, where one or more H atoms may be replaced by F, or anaromatic or heteroaromatic ring system having 5 to 12 aromatic ringatoms, which may in each case be substituted by one or more radicals R²;a plurality of radicals R¹ here may also form a mono- or polycyclic,aliphatic, aromatic and/or benzo-fused ring system with one another.

The metal complexes according to the invention can in principle beprepared by various processes. However, the processes described belowhave proven particularly suitable.

The present invention therefore furthermore relates to a process for thepreparation of the metal-complex compounds of the formula (1) byreaction of the corresponding free ligands with metal alkoxides of theformula (344), with metal ketoketonates of the formula (345) or withmetal halides of the formula (346),

where the symbols M, n and R¹ have the meanings indicated above, andHal=F, Cl, Br or I.

It is likewise possible to use metal compounds, in particular iridiumcompounds, which carry both alcoholate and/or halide and/or hydroxylradicals as well as ketoketonate radicals. These compounds may also becharged. Corresponding iridium compounds which are particularly suitableas starting materials are disclosed in WO 2004/085449. [IrCl₂(acac)₂]⁻,for example Na[IrCl₂(acac)₂], is particularly suitable.

The complexes are preferably synthesised as described in WO 2002/060910and in WO 2004/085449. heteroleptic complexes can also be synthesised,for example, in accordance with WO 2005/042548. The synthesis can alsobe activated, for example, thermally, photochemically and/or bymicrowave radiation.

These processes enable the compounds of the formula (1) according to theinvention to be obtained in high purity, preferably greater than 99%(determined by means of ¹H-NMR and/or HPLC).

The synthetic methods explained here enable the preparation of, interalia, the compounds of the formulae (347) to (496) according to theinvention depicted below.

The complexes of the formula (1) described above and the preferredembodiments mentioned above can be used as active component in theelectronic device. An electronic device is taken to mean a device whichcomprises an anode, a cathode and at least one layer, where this layercomprises at least one organic or organometallic compound. Theelectronic device according to the invention thus comprises an anode, acathode and at least one layer which comprises at least one compound ofthe formula (1) indicated above. Preferred electronic devices here areselected from the group consisting of organic electroluminescent devices(OLEDs, PLEDs), organic integrated circuits (O-ICs), organicfield-effect transistors (O-FETs), organic thin-film transistors(O-TFTs), organic light-emitting transistors (O-LETs), organic solarcells (O-SCs), organic optical detectors, organic photoreceptors,organic field-quench devices (O-FQDs), light-emitting electrochemicalcells (LECs) or organic laser diodes (O-lasers), comprising, in at leastone layer, at least one compound of the formula (1) indicated above.Particular preference is given to organic electroluminescent devices.Active components are generally the organic or inorganic materials,which are introduced between the anode and cathode, for examplecharge-injection, charge-transport or charge-blocking materials, but inparticular emission materials and matrix materials. The compoundsaccording to the invention exhibit particularly good properties asemission material in organic electroluminescent devices. Organicelectroluminescent devices are therefore a preferred embodiment of theinvention.

The organic electroluminescent device comprises a cathode, an anode andat least one emitting layer. Apart from these layers, it may alsocomprise further layers, for example in each case one or morehole-injection layers, hole-transport layers, hole-blocking layers,electron-transport layers, electron-injection layers, exciton-blockinglayers, charge-generation layers and/or organic or inorganic p/njunctions. It is likewise possible for interlayers, which have, forexample, an exciton-blocking function and/or control the charge balancein the electroluminescent device, to be introduced between two emittinglayers. However, it should be pointed out that each of these layers doesnot necessarily have to be present. The organic electroluminescentdevice may comprise one emitting layer or a plurality of emittinglayers. If a plurality of emission layers are present, these preferablyhave in total a plurality of emission maxima between 380 nm and 750 nm,resulting overall in white emission, i.e. various emitting compoundswhich are able to fluoresce or phosphoresce are used in the emittinglayers. Particular preference is given to three-layer systems, where thethree layers exhibit blue, green and orange or red emission (for thebasic structure see, for example, WO 05/011013), or systems whichcomprise more than three emitting layers.

In a preferred embodiment of the invention, the organicelectroluminescent device comprises the compound of the formula (1) orthe preferred embodiments mentioned above as emitting compound in one ormore emitting layers.

If the compound of the formula (1) is employed as emitting compound inan emitting layer, it is preferably employed in combination with one ormore matrix materials. The mixture of the compound of the formula (1)and the matrix material comprises between 0.1 and 99% by weight,preferably between 0.5 and 40% by weight, particularly preferablybetween 1 and 30% by weight, in particular between 2 and 25% by weight,of the compound of the formula (1), based on the entire mixturecomprising emitter and matrix material. Correspondingly, the mixturecomprises between 99 and 1% by weight, preferably between 98 and 60% byweight, particularly preferably between 97 and 70% by weight, inparticular between 95 and 75% by weight, of the matrix material, basedon the entire mixture comprising emitter and matrix material.

Suitable matrix materials for the compounds according to the inventionare ketones, phosphine oxides, sulfoxides and sulfones, for example inaccordance with WO 2004/013080, WO 2004/093207, WO 2006/005627 or DE102008033943.1, triarylamines, carbazole derivatives, for example CBP(N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO05/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO2008/086851, indolocarbazole derivatives, for example in accordance withWO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, forexample in accordance with the applications DE 102009023155.2 and DE102009031021.5, azacarbazoles, for example in accordance with EP1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrixmaterials, for example in accordance with WO 2007/137725, silanes, forexample in accordance with WO 2005/111172, azaboroles or boronic esters,for example in accordance with WO 06/117052, triazine derivatives, forexample in accordance with the application DE 102008036982.9, WO2007/063754 or WO 2008/056746, zinc complexes, for example in accordancewith EP 652273 or in accordance with WO 2009/062578, diaza- ortetraazasilole derivatives, for example in accordance with DE102008056688.8, or diazaphosphole derivatives, for example in accordancewith DE 102009022858.6.

It may also be preferred to employ a plurality of different matrixmaterials as a mixture, in particular at least one electron-conductingmatrix material and at least one hole-conducting matrix material. Apreferred combination is, for example, the use of an aromatic ketone ora triazine with a triarylamine derivative or a carbazole derivative asmixed matrix for the metal complex according to the invention.Preference is likewise also given to mixtures of a hole- orelectron-transporting material with a material which is involved inneither hole transport nor electron transport, as disclosed, forexample, in DE 102009014513.3.

In a further preferred embodiment of the present invention, thecompounds according to the invention can be employed in mixtures withone or more further emitters. Very particular preference is given hereto a mixture of the compounds according to the invention with one ormore fluorescent emitters. Preference is furthermore given to a mixturewith one or more phosphorescent emitters. fluorescent emitters emitprincipally from excited singlet states, whereas phosphorescent emittersemit light principally from higher spin states (for example triplet andquintet). For the purposes of this invention, the complexes of organictransition metals are taken to be phosphorescent emitters. The furtheremitters are preferably organic compounds.

In a particularly preferred embodiment of the present invention, thecompounds according to the invention are mixed with 3 further emitters,in a particularly preferred embodiment with 2 further emitters and in anespecially very preferred embodiment with one further emitter.

In a further preferred embodiment of the present invention, the emittermixtures comprise 3, particularly preferably 2 and very particularlypreferably one compound according to the invention.

In a particularly preferred embodiment of the present invention, theemitter mixtures comprise precisely one of the compounds according tothe invention and precisely one further emitter.

It is furthermore preferred for the purposes of the present inventionfor the absorption spectra of at least one emitter and the emissionspectrum of at least one other emitter of the mixture to overlap,simplifying energy transfer (double doping) between the emitters. Theenergy transfer here can take place by various mechanisms.Non-definitive examples of this are Förster or Dexter energy transfer.

The emitter mixtures described preferably comprise at least two emitterswhich both emit red light. Preference is furthermore given to emittermixtures comprising at least one emitter which emits red light and atleast one emitter which emits green light.

The cathode preferably comprises metals having a low work function,metal alloys or multilayered structures comprising various metals, suchas, for example, alkaline-earth metals, alkali metals, main-group metalsor lanthanoids (for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alsosuitable are alloys of an alkali or alkaline-earth metal and silver, forexample an alloy of magnesium and silver. In the case of multilayeredstructures, further metals which have a relatively high work function,such as, for example, Ag, may also be used in addition to the saidmetals, in which case combinations of the metals, such as, for example,Ca/Ag or Ba/Ag, are generally used. It may also be preferred tointroduce a thin interlayer of a material having a high dielectricconstant between a metallic cathode and the organic semiconductor.Suitable for this purpose are, for example, alkali metal oralkaline-earth metal fluorides, but also the corresponding oxides orcarbonates (for example LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.).The layer thickness of this layer is preferably between 0.5 and 5 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiO_(x),Al/PtO_(x)) may also be preferred. For some applications, at least oneof the electrodes must be transparent in order to enable eitherirradiation of the organic material (O-SCs) or the coupling-out of light(OLEDs/PLEDs, O-lasers). A preferred structure uses a transparent anode.Preferred anode materials here are conductive mixed metal oxides.Particular preference is given to indium tin oxide (ITO) or indium zincoxide (IZO). Preference is furthermore given to conductive doped organicmaterials, in particular conductive doped polymers.

In general, all materials as used for the layers in accordance with theprior art can be used in the further layers, and the person skilled inthe art will be able to combine each of these materials with thematerials according to the invention in an electronic device withoutinventive step.

The device is correspondingly (depending on the application) structured,provided with contacts and finally hermetically sealed, since thelifetime of devices of this type is drastically shortened in thepresence of water and/or air.

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are applied by means of asublimation process, in which the materials are vapour-deposited invacuum sublimation units at an initial pressure of usually less than10⁻⁵ mbar, preferably less than 10⁻⁶ mbar. It is also possible for theinitial pressure to be even lower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are applied by means of theOVPD (organic vapour phase deposition) process or with the aid ofcarrier-gas sublimation, in which the materials are applied at apressure between 10⁻⁵ mbar and 1 bar. A special case of this process isthe OVJP (organic vapour jet printing) process, in which the materialsare applied directly through a nozzle and thus structured (for exampleM. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting or offset printing, but particularly preferably LITI (lightinduced thermal imaging, thermal transfer printing) or ink-jet printing.Since the compounds of the formula (1) according to the invention havevery good solubility in organic solvents, they are particularly suitablefor processing from solution.

The organic electroluminescent device can also be produced as a hybridsystem by applying one or more layers from solution and applying one ormore other layers by vapour deposition. Thus, for example, it ispossible to apply an emitting layer comprising a compound of the formula(1) and a matrix material from solution and to apply a hole-blockinglayer and/or an electron-transport layer on top by vacuum vapourdeposition.

These processes are generally known to the person skilled in the art andcan be applied by him without problems to organic electroluminescentdevices comprising compounds of the formula (1) or the preferredembodiments mentioned above.

For processing from solution, solutions or formulations of the compoundsof the formula (1) are necessary. It may also be preferred to usemixtures of two or more solvents. Suitable and preferred solvents are,for example, toluene, anisole, o-, m- or p-xylenes, methyl benzoate,dimethylanisoles, mesitylenes, tetralin, veratrol, tetrahydrofuran(THF), methyl-THF, THP, chlorobenzene, dioxane, or mixtures of thesesolvents.

The present invention therefore furthermore relates to a solution orformulation comprising at least one compound of the formula (1) and oneor more solvents, in particular organic solvents. The way in whichsolutions of this type can be prepared is known to the person skilled inthe art and is described, for example, in WO 02/072714, WO 2003/019694and the literature cited therein.

The electronic devices according to the invention, in particular organicelectroluminescent devices, are distinguished by the followingsurprising advantages over the prior art:

-   1. The compounds of the formula (1) have very good solubility in a    multiplicity of common organic solvents and are therefore very    highly suitable for processing from solution. In particular, the    compounds according to the invention have higher solubility than the    similar compounds described in the prior art.-   2. Organic electroluminescent devices comprising compounds of the    formula (1) as emitting materials have an excellent lifetime. In    particular, the lifetime is better than in the case of similar    compounds in accordance with the prior art.-   3. Organic electroluminescent devices comprising compounds of the    formula (1) as emitting materials have excellent efficiency. In    particular, the efficiency is better than in the case of similar    compounds in accordance with the prior art.

These above-mentioned advantages are not accompanied by an impairment inthe other electronic properties.

The compounds according to the invention are capable of emitting lightunder certain prerequisites. These compounds are thus very versatile.Some of the principal areas of application here are display orillumination technologies. It is furthermore particularly advantageousto employ the compounds and devices comprising these compounds in thearea of phototherapy.

The present invention therefore furthermore relates to the use of thecompounds according to the invention and devices comprising thecompounds for the treatment, prophylaxis and diagnosis of diseases. Thepresent invention still furthermore relates to the use of the compoundsaccording to the invention and devices comprising the compounds for thetreatment and prophylaxis of cosmetic conditions.

The present invention furthermore relates to the use of the compoundsaccording to the invention for the production of devices for thetherapy, prophylaxis and/or diagnosis of therapeutic diseases.

Phototherapy or light therapy is used in many medical and/or cosmeticareas. The compounds according to the invention and the devicescomprising these compounds can therefore be employed for the therapyand/or prophylaxis and/or diagnosis of all diseases and/or in cosmeticapplications for which the person skilled in the art considers the useof phototherapy. Besides irradiation, the term phototherapy alsoincludes photodynamic therapy (PDT) and disinfection and sterilisationin general. Phototherapy or light therapy can be used for the treatmentof not only humans or animals, but also any other type of living ornon-living materials. These include, for example, fungi, bacteria,microbes, viruses, eukaryotes, prokaryotes, foods, drinks, water anddrinking water.

The term phototherapy also includes any type of combination of lighttherapy and other types of therapy, such as, for example, treatment withactive compounds. Many light therapies have the aim of irradiating ortreating exterior parts of an object, such as the skin of humans andanimals, wounds, mucous membranes, the eye, hair, nails, the nail bed,gums and the tongue. The treatment or irradiation according to theinvention can in addition also be carried out inside an object in order,for example, to treat internal organs (heart, lung, etc.) or bloodvessels or the breast.

The therapeutic and/or cosmetic areas of application according to theinvention are preferably selected from the group of skin diseases andskin-associated diseases or changes or conditions, such as, for example,psoriasis, skin ageing, skin wrinkling, skin rejuvenation, enlarged skinpores, cellulite, oily/greasy skin, folliculitis, actinic keratosis,precancerous actinic keratosis, skin lesions, sun-damaged andsun-stressed skin, crows' feet, skin ulcers, acne, acne rosacea, scarscaused by acne, acne bacteria, photomodulation of greasy/oily sebaceousglands and their surrounding tissue, jaundice, jaundice of the newborn,vitiligo, skin cancer, skin tumours, Crigler-Najjar, dermatitis, atopicdermatitis, diabetic skin ulcers and desensitisation of the skin.

Particular preference is given for the purposes of the invention to thetreatment and/or prophylaxis of psoriasis, acne, cellulite, skinwrinkling, skin ageing, jaundice and vitiligo.

Further areas of application according to the invention for thecompositions and/or devices comprising the compositions according to theinvention are selected from the group of inflammatory diseases,rheumatoid arthritis, pain therapy, treatment of wounds, neurologicaldiseases and conditions, oedema, Paget's disease, primary andmetastasising tumours, connective-tissue diseases or changes, changes inthe collagen, fibroblasts and cell level originating from fibroblasts intissues of mammals, irradiation of the retina, neovascular andhypertrophic diseases, allergic reactions, irradiation of therespiratory tract, sweating, ocular neovascular diseases, viralinfections, particularly infections caused by herpes simplex or HPV(human papillomaviruses) for the treatment of warts and genital warts.

Particular preference is given for the purposes of the invention to thetreatment and/or prophylaxis of rheumatoid arthritis, viral infectionsand pain.

Further areas of application according to the invention for thecompounds and/or devices comprising the compounds according to theinvention are selected from winter depression, sleeping sickness,irradiation for improving the mood, the reduction in pain, particularlymuscular pain caused by, for example, tension or joint pain, eliminationof the stiffness of joints and the whitening of the teeth (bleaching).

Further areas of application according to the invention for thecompounds and/or devices comprising the compounds according to theinvention are selected from the group of disinfections. The compoundsaccording to the invention and/or the devices according to the inventioncan be used for the treatment of any type of objects (non-livingmaterials) or subjects (living materials such as, for example, humansand animals) for the purposes of disinfection. This includes, forexample, the disinfection of wounds, the reduction in bacteria, thedisinfection of surgical instruments or other articles, the disinfectionof foods, of liquids, in particular water, drinking water and otherdrinks, the disinfection of mucous membranes and gums and teeth.Disinfection here is taken to mean the reduction in the livingmicrobiological causative agents of undesired effects, such as bacteriaand germs.

For the purposes of the phototherapy mentioned above, devices comprisingthe compounds according to the invention preferably emit light having awavelength between 250 and 1250 nm, particularly preferably between 300and 1000 nm and especially preferably between 400 and 850 nm.

In a particularly preferred embodiment of the present invention, thecompounds according to the invention are employed in an organiclight-emitting diode (OLED) or an organic light-emitting electrochemicalcell (OLEC) for the purposes of phototherapy. Both the OLED and the OLECcan have a planar or fibre-like structure having any desired crosssection (for example round, oval, polygonal, square) with a single- ormultilayered structure. These OLECs and/or OLEDs can be installed inother devices which comprise further mechanical, adhesive and/orelectronic elements (for example battery and/or control unit foradjustment of the irradiation times, intensities and wavelengths). Thesedevices comprising the OLECs and/or OLEDs according to the invention arepreferably selected from the group comprising plasters, pads, tapes,bandages, cuffs, blankets, caps, sleeping bags, textiles and stents.

The use of the said devices for the said therapeutic and/or cosmeticpurpose is particularly advantageous compared with the prior art, sincehomogeneous irradiation of lower irradiation intensity is possible atvirtually any site and at any time of day with the aid of the devicesaccording to the invention using the OLEDs and/or OLECs. The irradiationcan be carried out as an inpatient, as an outpatient and/or by thepatient themselves, i.e. without initiation by medical or cosmeticspecialists. Thus, for example, plasters can be worn under clothing, sothat irradiation is also possible during working hours, in leisure timeor during sleep. Complex inpatient/outpatient treatments can in manycases be avoided or their frequency reduced. The devices according tothe invention may be intended for reuse or be disposable articles, whichcan be disposed of after use once, twice or three times.

Further advantages over the prior art are, for example, lower evolutionof heat and emotional aspects. Thus, newborn being treated owing tojaundice typically have to be irradiated blindfolded in an incubatorwithout physical contact with the parents, which represents an emotionalstress situation for parents and newborn. With the aid of a blanketaccording to the invention comprising the OLEDs and/or OLECs accordingto the invention, the emotional stress can be reduced significantly. Inaddition, better temperature control of the child is possible due toreduced heat production of the devices according to the inventioncompared with conventional irradiation equipment.

It should be pointed out that variations of the embodiments described inthe present invention fall within the scope of this invention. Eachfeature disclosed in the present invention can, unless explicitlyexcluded, be replaced by alternative features which serve the same, anequivalent or a similar purpose. Thus, each feature disclosed in thepresent invention should, unless stated otherwise, be regarded as anexample of a generic series or as an equivalent or similar feature.

All features of the present invention can be combined with one anotherin any way, unless certain features and/or steps are mutually exclusive.This applies, in particular, to preferred features of the presentinvention. Equally, features of non-essential combinations can be usedseparately (and not in combination).

It should furthermore be pointed out that many of the features, and inparticular those of the preferred embodiments of the present invention,should be regarded as inventive themselves and not merely as part of theembodiments of the present invention. Independent protection may begranted for these features in addition or as an alternative to eachinvention claimed at present.

The teaching regarding technical action disclosed with the presentinvention can be abstracted and combined with other examples.

The invention is explained in greater detail by the following exampleswithout wishing it to be restricted thereby.

EXAMPLES

The following syntheses are carried out, unless indicated otherwise,under a protective-gas atmosphere in dried solvents. The startingmaterials II and IV are commercially available (for example from VWRChemikalien). Compounds I and VIII can be prepared analogously to thosein WO 02/068435. Compound VI can be prepared in accordance with Organicletters, 2005, 7, 19, 4277-4280.

Example 1 Preparation of compound T1

Synthetic Procedure for the Preparation of Compound T1:

5.0 g (4.8 mmol) of compound I, and 1.1 g (5.3 mmol) of potassiumacetate are suspended in 100 ml of degassed dimethylacetamide. 11 mg(0.05 mmol) of Pd(OAc)₂ are added to this suspension. 2.7 g (14.4 mmol)of compound II are added. The reaction mixture is heated under refluxfor 4 days. After cooling, the reaction solution is poured into 175 mlof water. 200 ml of dichloromethane are then added. The organic phase isseparated off, washed three times with 75 ml of water and subsequentlyevaporated to dryness. The residue is washed with ethanol andrecrystallised from toluene and finally dried under reduced pressure.The yield is 5.3 g (3.9 mmol), corresponding to 80.7% of theory.

Example 2 Preparation of Compound T2

Synthetic Procedure for the Preparation of Compound T2:

The synthesis is carried out analogously to that of compound T1 inExample 1 using 5.0 g (4.8 mmol) of compound I, where compound II isreplaced by 3.1 g (14.4 mmol) of compound IV. The yield is 5.9 g (4.1mmol), corresponding to 85.2% of theory.

Example 3 Preparation of Compound T3

Synthetic Procedure for the Preparation of Compound T3

The synthesis is carried out analogously to that of compound T1 inExample 1 using 5.0 g (4.8 mmol) of compound I, where compound II isreplaced by 3.9 g (14.4 mmol) of compound VI. The yield is 5.3 g (3.3mmol), corresponding to 68.8% of theory.

Example 4 Preparation of Compound T4

Synthetic Procedure for the Preparation of Compound T4:

The synthesis is carried out analogously to that of compound T1 inExample 1 using 2.7 g (14.4 mmol) of compound II, where compound I isreplaced by 5.0 g (4.8 mmol) of compound VIII. The yield is 5.1 g (3.7mmol), corresponding to 77.9% of theory.

Example 5 Preparation of Compound T5

Synthetic Procedure for the Preparation of Compound T5:

3.8 g (14.6 mmol) of N-(phenylsulfonyl)-3-phenyloxaziridine are added toa solution of 6.0 g (4.4 mmol) of compound T1 in 100 ml ofdichloromethane. The reaction mixture is stirred at room temperature for20 h. The evaporated residue is purified through a silica-gel column.The solid is recrystallised from toluene and dried under reducedpressure. The yield is 1.6 g (1.1 mmol), corresponding to 25.4% oftheory.

Example 6 Preparation of Compound T6

Synthetic Procedure for the Preparation of Compound T6:

7.5 g (5.3 mmol) of compound T5 and 3.2 g (8.0 mmol) of2,4-bis-(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide(Lawesson's reagent) are suspended in 100 ml of degassed toluene. Thesuspension is heated under reflux for 20 h. After cooling, the reactionmixture is filtered off. The solid is recrystallised from toluene. Theyield is 5.1 g (3.5 mmol), corresponding to 65.2% of theory

Examples 7 to 12 Production and Characterisation of OrganicElectroluminescent Devices Comprising the Compounds According to theInvention

The structures of matrix materials TMM-1 (synthesised in accordance withDE 102008036982) and TMM-2 (synthesised in accordance with DE102008017591) used below are depicted below.

The materials according to the invention can be used from solution,where they result in devices having good properties which are simple toproduce. The production of such components is based on the production ofpolymeric light-emitting diodes (PLEDs), which has already beendescribed many times in the literature (for example in WO 2004/037887).In the present case, compounds T1 to T6 according to the invention aredissolved in toluene. The typical solids content of such solutions isbetween 16 and 25 g/l if, as here, the typical layer thickness of 80 nmfor a device is to be achieved by means of spin coating. Theelectroluminescent device used exhibits the following structure:ITO/PEDOT:PSS/interlayer/EML/cathode, where EML represents the emissionlayer. Structured ITO substrates and the material for the so-calledbuffer layer (PEDOT, more accurately PEDOT:PSS) are commerciallyavailable (ITO from Technoprint and others, PEDOT:PSS as Clevios BaytronP aqueous dispersion from H.C. Starck). The interlayer used serves forhole injection; in this case, HIL-012 from Merck KGaA, Germany, wasused. The emission layer is applied by spin coating in an inert-gasatmosphere, in the present case argon, and dried by heating at 120° C.for 10 min. Finally, a barium and aluminium cathode is applied by vacuumvapour deposition. A hole-blocking layer and/or an electron-transportlayer can also be applied between the emitting layer (EML) and thecathode by vapour deposition. Furthermore, the interlayer may also bereplaced by one or more layers, which merely have to satisfy thecondition of not being detached again by the subsequent processing stepof deposition of the emitting layer from solution.

The devices are characterised by in a standard manner by means ofmethods which are well known to the average person skilled in the art inthe area. However, the OLEDs mentioned here have not yet been optimised.Table 1 summarises the data obtained. In the case of the processeddevices, it is apparent that the materials according to the inventionare superior to those previously available in efficiency and/orlifetime.

TABLE 1 Results with solution-processed materials in the deviceconfiguration: ITO/PEDOT:PSS/interlayer/EML/cathode Max. VoltageLifetime [h], eff. [V] initial EML [cd/ at CIE luminance Ex. 80 nm A]100 cd/m² (x/y) 1000 cd/m² 7 TMM-1:TMM-2:T-1 8 5.1 0.66/0.33 6500 8TMM-1:TMM-2:T-2 7 5.0 0.67/0.33 8000 9 TMM-1:TMM-2:T-3 7 4.9 0.65/0.3210000 10 TMM-1:TMM-2:T-4 10 5.3 0.61/0.38 10500 11 TMM-1:TMM-2:T-5 8 5.20.67/0.33 15000 12 TMM-1:TMM-2:T-6 7 5.3 0.67/0.33 12000

The invention claimed is:
 1. A compound of the formula (1)M(L)_(n)(L′)_(m)  formula (1) where the compound contains a moietyM(L)_(n) is selected from the formulae (36) to (59)

wherein X is CR¹; R¹ is, identically or differently on each occurrence,H, D, F, Cl, Br, I, N(R²)₂, CN, NO₂, Si(R²)₃, B(OR²)₂, C(═O)R²,P(═O)(R²)₂, S(═O)R², S(═O)₂R², OSO₂R², a straight-chain alkyl, alkoxy orthioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl oralkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl,alkenyl, alkynyl, alkoxy, alkylakoxy or thioalkoxy group having 3 to 40C atoms, each of which is optionally substituted by one or more radicalsR², where one or more non-adjacent CH₂ groups is optionally replaced byR²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se, C═NR²,P(═O)(R²), SO₂, NR², O, S or CONR² and where one or more H atoms isoptionally replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, whichoptionally in each case is substituted by one or more radicals R², or anaryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which is optionally substituted by one or moreradicals R², or a diarylamino group, diheteroarylamino group oraryiheteroarylamino group having 10 to 40 aromatic ring atoms, which isoptionally substituted by one or more radicals R², or a combination oftwo or more of these groups; two or more radicals R¹ here may also forma mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ringsystem with one another; M is iridium or platinum; L′ is, identically ordifferently on each occurrence, a co-ligand; W is, identically ordifferently on each occurrence, a radical of the formulae (3) and (4)

where V is equal to S or O; R⁴ is, identically or differently on eachoccurrence, H, D, F, Cl, Br, I, N(R²)₂, a straight-chain alkyl, alkoxyor thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenylor alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl,alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40C atoms, each of which is optionally substituted by one or more radicalsR², where one or more non-adjacent CH₂ groups is optionally replaced byR²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se, C═NR²,P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more H atoms isoptionally replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, whichoptionally in each case is substituted by one or more radicals R², or anaryloxy, arylalkoxy, alkylaryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which is optionally substituted by one or moreradicals R², or a diarylamino group, diheteroarylamino group orarylheteroarylamino group having 10 to 40 aromatic ring atoms, which isoptionally substituted by one or more radicals R², or a combination oftwo or more of these groups; two or more radicals R⁴ here may also forma mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ringsystem with one another; R² is, identically or differently on eachoccurrence, H, D, F, Cl, Br, I, N(R³)₂, CN, NO₂, Si(R³)₃, B(OR³)₂,C(═O)R³, P(═O)(R³)₂, S(═O)R³, S(═O)₂R³, OSO₂R³, a straight-chain alkyl,alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chainalkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclicalkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having3 to 40 C atoms, each of which is optionally substituted by one or moreradicals R³, where one or more non-adjacent CH₂ groups is optionallyreplaced by R³C═CR³, C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se,C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and where one or more Hatoms is optionally replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which optionally in each case is substituted by one or moreradicals R³, or an aryloxy, arylalkoxy, alkylaryloxy or heteroaryloxygroup having 5 to 60 aromatic ring atoms, which is optionallysubstituted by one or more radicals R³, or a diarylamino group,diheteroarylamino group or arylheteroarylamino group having 10 to 40aromatic ring atoms, which is optionally substituted by one or moreradicals R³, or a combination of two or more of these groups; two ormore adjacent radicals R² here may form a mono- or polycyclic, aliphaticor aromatic ring system with one another; R³ is, identically ordifferently on each occurrence, H, D, F or an aliphatic, aromatic and/orheteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, inaddition, one or more H atoms is optionally replaced by F; two or moresubstituents R³ here optionally also forms a mono- or polycyclic,aliphatic or aromatic ring system with one another; n is 1, 2 or 3 for Mequal to iridium and is 1 or 2 for M equal to platinum; m is 0, 1, 2 forM equal to iridium and is 0 or 1 for M equal to platinum; the indices nand m here are selected so that the coordination number on the metalcorresponds to 6 for M equal to iridium or rhodium and corresponds to 4for M equal to platinum or palladium.
 2. The compound according to claim1, wherein the moiety M(L)_(n) is selected from the formulae (36), (40),(44), (48), (52), and (56).
 3. The compound according to claim 1,wherein the radical W is given by the formulae (110) to (115)

where R⁵ is, identically or differently on each occurrence, H, D, astraight-chain alkyl or thioalkoxy group having 1 to 40 C atoms or astraight-chain alkenyl or alkynyl group having 2 to 40 C atoms or abranched or cyclic alkyl, alkenyl, alkynyl or thioalkoxy group having 3to 40 C atoms, each of which is optionally substituted by one or moreradicals R², where one or more non-adjacent CH₂ groups is optionallyreplaced by R²C═CR², C≡C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se,C═NR², P(═O)(R²), SO, SO₂, NR², O, S or CONR² and where one or more Hatoms is optionally replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which optionally in each case is substituted by one or moreradicals R², or an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which is optionally substituted by one or moreradicals R², or a diarylamino group, diheteroarylamino group orarylheteroarylamino group having 10 to 40 aromatic ring atoms, which isoptionally substituted by one or more radicals R², or a combination oftwo or more of these groups; two or more radicals R¹ here optionallyalso forms a mono- or polycyclic, aliphatic, aromatic and/or benzo-fusedring system with one another.
 4. The compound according to claim 1,wherein M is equal to iridium.
 5. The compound according to claim 1,wherein m=0.
 6. A process for the preparation of the compound accordingto claim 1 which comprises reacting the corresponding free ligands withmetal alkoxides of the formula (344), with metal ketoketonates of theformula (345) or with metal halides of the formula (346)

where the symbols M, n and R¹ have the meanings indicated in claim 1 andHal=F, Cl, Br or I.
 7. A formulation comprising at least one compoundaccording to claim 1 and at least one solvent.